Coloration of textile materials



Patented Apr. 16, 1940 COLORATION F TEXTILE MATERIALS George Holland Ellis, Charles Finley Topham, and Henry Charles OlDin, Spondon, near Derby, England, assignors to Celanese Corporation of America, a corporation of Delaware No Drawing. Application December 28, 1937, Se-

rial No. 182,166. In Great Britain November 11 Claims.

This invention relates to the coloration of cellulose acetate and other cellulose ester or ether filaments, straws, films and the like, and especially to a method for the production of deep di- (hydroxyethyl) -2 5-dimethoxy aniline. The N-di-(hydroxyethyl) -meta-toluidine has been found of particular value.

If desired the hydroxyl groups of the hydroxyallwl-aniline coupling components may be etherified or esterified. Again, where two or more hydroxy groups are present one hydroxy group may be in the free state and another etherifled, e. g., by a methyl group, or esterified, e. g., by

2 4-dinitro- 6 -chlor-benzene-azo- 4-amino-2'- methyl-5'-methoxy-benzene.

4 -nitro-benzene-azo- 4' -amino-2' 5'-dimethylbenzene.

4-amino-4'-dimethylamino-azobenzene.'

shades on these products. an acetyl group. 5

According to .the present invention the afore- Diazo components suitable for the purposes of said cellulose ester or ether materials are colored the invention are azo-benzenes, azo-a-naphthaby forming a substantially water-insoluble azo nes and be n -azo-u-nap th s ntaindye thereon from a diazotized amino-azo comg o or WO zot able m no groups in P pound and an N-hydroxyalkyl aniline capable positions to azo groups. Substituents may be 10 of coupling with a diazo compound in para popresent in addition to the diazotisable amino sition to the hydroxyalkylamino group. In this groups and e two groups, o example alkyl way it is possible to obtain economically a wide ups, a k y r ups, 8. m th xy or eth xy range of deep shades, particularly blacks, navy roup hal n at m or nitro group he la blues, and browns, which have an excellent fast- W types of Substituents more P rly ness to light. I relati t th d th of h d in a nucleus which does not contain a diazotisobtainable the proportions of the diazo coupling a amino p- Sulphonio and oalboxylio components required based on the weight of the ps should be absentmaterial is low. Such deep shades are difllcult Particular Value for the P p s o the to obtain by direct dyeing methods and then only invention are diazo components of the general by the use of undesirably large proportions of formula colon'ng matter based on the weight of the max terial; moreover the fastness to rubbing is frequently very poor. NOON: NHI

Hydroxyethyl groups are particularly suitable as the hydroxyalkyl substituent of the N-hy- Z droxyalkyl aniline employed as the coupling comw n X ep e ts yd o e y, alkyl ponent. Other hydroxyalkyl groups may be util en. Y r p s n -lk y. al y halogen or lised, however, e. g., the hydroxy-propyl group, aoidylemino n Z r p n hydrogen or halothe p-y-dihydroxy-propyl group, or the -chlore S amino-5Z0 compounds eon readily be p-hydroxy-propyl group. The benzene nuclei f prepared by coupling diazotised para-nitraniline, the hydroxyalkyl anilines may contain substituor t e appr priate halogen derivat ve the o entsin addition to the hydroxyalkylamino groups. With the pp p a y su u ed aniline, 8-, For example alkyl or alkoxy groups may be presmete-toluidine, oresidine, P -Kyl din or 2 ent in the 3-positions of the benzene nuclei or dimethoxy-om'linein both the 3- and 6-positions of the said nuclei. The following are examples of diazo p 3Again, halogen atoms may be present in the Ilents W i h y e mp y -positions of the nuclei.

The hydroxyalkyl aniline coupling component Amnmalzomarzhthalene' ma have eithe on r t h d m Benzene azo-u naphthylamine.

y b H t e 0 5 y roxya Y1 ,gmups 2-methoxy-benzene-azo-a-naphthylamme. '40 as 5 1 uen s m the ammo gmup- Agam the 4-- nitro-benzene-azo- 4' -amino- 2' -methyl- 5' amino group may carry both a hydroxyalkyl methoxwbenzena group and another substituent, for example an 2 1 b -azo-4'-amino-2'-methunsubstituted alkyl group, a cyclo-alkyl group or an aralkyl group e g meth l eth l l y! 5 -methoxy-benzene' hexyl benzyl f cyc 4-gtro-benzene-azo-4'-amino-2' :5'-d1methoxynzene. specific coupling components which can be used according to the invention are 4-n1tro-2-chlor-benzene-azo-4 amino-2 5 di droxyethyl) -aniline N-di-(h drox th l)- nPethQxybenzene' y Y y meta- 4-n1tro-2-methoxy-benzene-azo-4'-ammo-2' 5'- toluidine, N-d1-(hydroxyethyl) -cres1d1ne, and N- dimethoxybenzene' 4-amino-4'-diethylamino-azobenzene.

2 -methoxy- 4 -amino-4-dimethylamino-azobenzene.

2-methoxy-4-amino-4'-diethylamino-azobenzene.

4 -amino 4 di-(hydroxyethyl) -amino-azobenzene.

4-amino-4 -dihydroxyethyl) azobenzene.

4 -amino- 4'-di- (hydroxyethyl) -amino azobenzene.

2 -chlor- 4 -aminoazobenzene.

2-chlor-4-amino-4'-di (hydroxyethyl) -amino- 2'- methyl-azobenzene.

4 :4 -diamino-3 :G-dimethyl-azobenzene.

4 :4 -diamino-8 -methoxy-6-methyl-azobenzene.

4 4-diamino-2'-chlor-3-methoxy-6-methyl-azobenzene.

4 4 -diamino-3 6 -dimethoxy-azobenzene.

4 4'-diamino- 2' -chlor-3 fi-dimethoxy-azobenzene.

4-amino-benzene-azo-a-naphthylamine.

We have further found that valuable colorations may also be obtained by using as the diazo component instead of an amino-azo compound a para-amino diarylamine. Examples of such compounds are, for instance, 4-amino4'-methoxyor ethoxy-diphenylamine, 4:4-diamino-diphenylamine, and l-aminoor l-alkylaminoor 1 hydroxy-alkylamino-4 -(4'-amino-pheny1amino) -anthraquinones, for example l-methylamino 4 -(4' amino-phenylamino) -anthraquinone. This latter compound yields with di-(hydroxyethyl) -metatoluidine valuable green shades.

The following table shows the shades obtainable on cellulose acetate from certain combinations of diazo component and coupling component in accordance with the invention:

-amino-2'-methyl- 2'-chlor- 4' -di- (hydroxyethyl) -amino- Diazo component I examples:

Example 1 20 parts of finely milled 10% aqueous paste of 4-nitro -2- chlor-benzene-azo-4-amino-2'-methyl-5-methoxybenzene is dispersed in 3,000 parts of water with the aid of soap and Turkey red oil. 100 parts of cellulose acetate fabric is dyed in this bath at '78 to 80 C. for about 2 hours. The material is then lifted and diazotised for 30 minutes at ordinary temperature in a 15:1 bath containing 20% of concentrated hydrochloric acid and 5% of sodium nitrite based on the weight of the goods. The diazotised material is then washed well and worked in a bath of 2 parts of di-(hydroxyethyl) -metatoluidine in 3,000 parts of water and 0.75 part of soda ash first for 20 minutes in the cold, then for 20 minutes while heating up to 60 C. and finally for half an hour at 60 C. The fabric is A full reddish blue shade is thus obtained.

' Example 2 parts of a cellulose acetate fabric is dyed in the manner described in Example 1 but using Amiuo-azo-naphthaleno o 2-m ethoxybenzene-azo e-naphtbylamin 4-nlg-bcnzene-azc-4-amino-2'-methyl-5'-methoxybenzenc o 4-nitro-2-chlorbenzene-azo4'-amino-2methyl-5'-methoxybenzcn 4-nitroben 1.ene-azo4'-amino-2 fi' dimethoxybenzene 4 4-diamm02-chlcr-3-methoxy fi-methylazobenzene 4 4'-diamino-3 fi'dimethoxy-azobenzene 4 4-diamino-2'-chlor-3 o-dimethoxy-azobenzene Coupling component Shade N-di-(hydroxyethyD-3-toluidinc Plum. N-di- (hydroxyethyl) -cresidine Do. Ndi-(hydroxyethyl;-2:5-dimethoxyaniline Black.

. N-di-(hydroxyethyl -3-toluldinc Maroon.

- N-di-(hydroxyethyD-aniline. Deep red.

N-di-(hydroxyethyl)-3-toluidine Maroon.

N-di-(hydroxyethyl)'cresidine" Do.

. N-di-(hydroxyethyl) -3-toluidine. Navy. ...do Black. ...do. Reddish black. ...do i Black. ..do Deep violet.

Preferably the components used are free from nuclear hydroxyl groups.

As regards the procedure to be followed in forming the azo dyes on the cellulose ester or ether materials, we prefer to incorporate the diazo component in the material and then to effect diazotisation and couple with a coupling component in a separate bath.

The diazo components can be applied to the materials in the form of aqueous dispersions. Bath methods may be employed, that is to say methods in which the materials are allowed to absorb the diazo component from an aqueous dispersion of the latter in which they are immersed. Again, mechanical impregnation methods may be used, the materials being impregnated with the requisite proportion of diazo component in an amount of liquid which is not greater than can be retained by the materials. To this end padding or printing methods may be utilised. The impregnated material may then be aged or steamed to cause the diazo component to enter the cellulose ester or ether material.

The reddish blue dyeing is then topped with 7 parts of a 10% aqueous paste of the azo dye from diazotized 6-ethoxy-2-aminobenzthiazol and N- hydroxyethyl-3 'I-dihydroxy- 1 :2 3 :4-tetrahydro o-naphthoquinoline. The material is thus dyed in a full navy blue, of excellent night shade, which is dischargeable to white by means of soluble zinc formaldehyde sulphoxylate.

The materials processed in accordance with the invention may be made from various cellulose esters or ethers, for example cellulose acetate, formate, propionate or butyrate, or methyl, ethyl or benzyl cellulose. The filaments or the like can be such as are directly produced by spinning solutions of cellulose esters or ethers or products which have been made by stretching already formed cellulose ester or ether filaments or the like in the presence of organic softening agents for the material, or in the presence of steam or hot water. Again, the cellulose esters or ethers may be those in which the cellulose has been esterifled, etherified, or both esterified and etherified to a high degree. Such products are then soaped and dried.

those made by esterifying formed filaments,yarns, foils, films and similar materials having a basis of organic derivatives of cellulose as described, for instance, in U. S. applications S. Nos. 39,288, 39,289 and 39,290, all filed September 5, 1935.

Particular mention may be made of the products obtainable by subjecting cellulose acetate textile materials to the action of acetic anhydride in the manner described in U. S. application S. No. 39,290.

The new process is also of value in the case of coloring the cellulose ester or ether in mixed materials containing both cellulose ester or ether and another material, for example silk, wool, cotton, or regenerated cellulose.

Having described our invention what we desire to secure by Letters Patent is:

1. Process for the coloration of cellulose ester or ether materials, which comprises coupling thereon a hydroxyalkyl aniline, capable of coupling in para position to the hydroxyalkylamino group, with a compound selected from the group consisting of diazotized amino-azo compounds of which the aromatic nuclei are all of the benzene series, diazotized amino-azo compounds of which the aromatic nuclei are all of the napthalene series, diazotized amino-azo compounds of which some of the aromatic-nuclei are of the benzene series while the others are of the naphthalene series, and diazotized amino diarylamines.

2. Process for the coloration of cellulose acetate materials, which comprises coupling thereon a diazotized monoamino-azo benzene with a hydroxyalkyl aniline capable of coupling in para position to the hydroxyalkylamino group.

3. Process for the coloration of cellulose ester or ether materials, which comprises coupling thereon a hydroxy-alkyl-aniline, capable of coupling in para position to the amino group and free from nuclear hydroxyl groups, with a diazotized amine of the formula NO N= QM.

wherein X represents a member of the group consisting of hydrogen, alkoxy, alkyl, and halogen, Y represents a member of the group consisting of alkoxy, alkyl, acidylamino and halogen, and Z represents a member of the group consisting of hydrogen and halogen.

5. Process for the coloration of cellulose ester 'or ether materials, which comprises coupling thereon di-(hydroxyethyl) -m-toluidine with a diazotized amine of the formula x NOQN= QNH:

7 NO N.

wherein X represents alkoxy, Y represents alkyl and Z represents hydrogen or halogen.

7. Process for the coloration of cellulose acetate materials, which comprises coupling thereon diazotized 4-nitro-2-chlorbenzene-azo-4'-amino-2'-. methyl-5'-methoxybenzene with di-(hydroxyethyl) -m-toluidine.

8. Process for the coloration of cellulose acetate materials, which comprises coupling thereon a di-(hydroxyalkyD-aniline capable of coupling in para position to the amino group and free from nuclear hydroxyl groups, with a diazotized ben- ZEUS-EZO-a-l'lfiDhthYlfiIlliIlG.

9. Process for the coloration of cellulose acetate materials, which comprises coupling thereon a di- (hydroxyalkyl) -aniline capable of coupling in para position to the amino group and free from nuclear hydroxyl groups, with diazotized i-nitro- 2-chlor-benzene-azo-a-naphthalamine.

10. Process for the coloration of cellulose acetate materials, which comprises coupling thereon di- (hydroxyethyl) -m-toluidine with diazotized 4- nitro-2-chlor-benzene-azo-a-naphthylamine.

11. Process for the coloration of cellulose acetate materials, which comprises coupling thereon di-(hydroxyethyl) -m-toluidine with diazotized 1- metlrylamino 4 (4' a min 0 phenylamino) anthraquinone.

GEORGE HOLLAND ELLIS. CHARLES FINLEY TOPHAM. HENRY CHARLES OLPIN.

CERTIFICATE OF CORRECTION. I Patent No. 2,196,98t. April 16, 191p.

' GEORGE HOLLAND ELLIS, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as'follows: Page 5, first 4 column, line 148, claim 5, for the word "groups" read --group--; and second column, lines 51; and55, claim '6, strike out "wherein X represents alkoxy, Y represents alkyl and Z represents hydrogen or halogen" and insert ins tead "wherein X represents a'member of the group consisting of hydrogen, alkoxy, alkyl, and halogen, Y represents .a member of the group consisting of alkoxy, allcyl, acidylamino and halogen, andZ represents amember of the group consisting of hydrogen and halogen-; and that the said Letters Patent should. be read with this correction therein that the same may conform to the rec-.

ord of the case in the Patent Office.

Signed and sealed this 25th day. of June, A. D. 191m.

A Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

